Dithiophosphonic acid esters and a process for their production



3,074,991 DITHIGPHOSPHGNIC ACE) ESTERS AND A PRCCESS FOR Tfllls PRQDUCTION Gerhard Schrader, Wnppertal-Cronenlierg, Germany, assignor to Farbenfahriiten Bayer Alrtiengesellschaft,

Leverlinsen, Germany, a corporation of Germany 'No Drawing. Fiied July 13, 1959, Ser. No. 82.6,4-53

Claims priority, application Germany July 29, 1958 3 Claims. (Cl. 260-461) The present invention relates to and has as its objects new and useful dithiop'hosphoric acid esters and a process for their production. The new compounds, which exhibit a remarkable insecticidal action, may be represented by the following general formula group by a further methyl radical.

These compounds which are the object of the present invention are obtained by reaction of corresponding dithiophosphonic acid-oralkyl esters with alk yl-vinyl-thioethers.

This reaction is to be ester and methyl vinyl ether as reactants:

be inventive formula s 002115 (CHa)2C=CH-I SCH-SC2H5 CH3 has been tested against caterpillars. Aqueous solutions of the aforesaid compound have been prepared by admix- .35 seen from the following equa- 'tion using methyl thiono-thiolphosphonic acid-O-methy-l 3,074,991 Patented darn. 2 2, i953 the same amount of an auxiliary solvent A commercial emulsifier (benzyl hydroxy ing it with (acetone). diphenyl polyglycol ether) is added in an amount of 20% This premixture then is referred to active ingredient.

The

diluted with water to the desired concentration. test has been carried out as follows:

Against caterpillars of the type diamond black moth (Pluteila maculipennis) 2' white cabbage has been spraye drip wet with aqueous emulsions as prepared above in a concentration as shown below. Caterpillars (10 each) have been placed on the sprayed leaves of the white cabbage. The living status of the caterpillars has been determined'a-fter 24 hours and 48 hours. The fol-lowing results have been obtained; 0.1 solutions killed caterpillars completely, 0.01% solutions killed caterpillars to The following examples are given to illustrate the process of the present invention.

49 grams (0.25 mol) of isobutenyl thionophosphonic- 'ethy-lv ester-thiol acid are dissolved in ml. of benzene. With stirring there are added dropwise 2 grams (0.25 mol) of ethyl vinyl ethyl ester. The temperature rises to about 65 C. Stirring is continued for 2 hours and the reaction product is then poured into water. The separated oil is taken up in benzene, washed neutral, and

dried over sodium sulfate. By fractionation 39 grams of the new ester with boiling point 97 C./ 0.01 mnL l-Ig are obtained. Yield 55% of the theoretical.

On rats per es the ester shows a medium-toxicity of 25 nag/kg.

By the same way but phosphonic ethyl ester-thiol molecular amount of vinyl thiol acid there is obtained ing formula using instead of isobutenyl thionoacid the corresponding equithionophosphonic ethyl esterthe compounds of the follow- Example 2 22 grams (0.25 mol.) of vinyl-thioethyl-ether are dissolved in 50 ml. of benzene. With stirring there are added to this solution 56 grams (0.25 mol) of cyclohexylthionophosphonic acid ethyl ester-thiolic acid. The temperature rises to 50 C. It is held at 50 C. for a further 2 hours and the reaction product is then poured into water. The precipitated oil is taken up with benzene, washed neutral with water, dried and held for a short time at a bath temperature of 70 C. under a pressure of 0.01 mm. in this way there are obtained 50 grams of the new ester as a pale yellow water-insoluble oil. Yield 64% of the theoretical.

By the same way but using instead of vinyl-thioethyl ether the corresponding molecular amount of vinyl-thiceral formula ing compounds S OCzHs S OCzHr S-(iH-S-CH:

CHa

3Q grams (0.25: mol.) of.

stirring 22 grams of (0.25 mol) of ethyl-vinylthioether in which R stands for a, member selected from the group are added. The mixture ,is stirred for another hour at a temperature of 60 C. andthen allowed to cool. The reaction product is washed in water. The benzene solution is separated and washed neutral with water. After drying over sodium sulfate' it is fractionated. 50 grams of the above compound are obtained of boiling point 78 C./0.01 mm. Hg; Yield 82% of the theoretical.

By the same way but using instead of methylthiono-O- ethyl-thiolphosphonic acid the corresponding equimolecularamountofethyl-thiono-0-methyl-thiolphosphonic. acid there is obtained the following compound I claim: 1'. A dithiophosphonic acid. ester. of the, following genconsisting of cycle alkyl and lower alkenyl, R and R stand for lower alkyl groups.

2. A compound of claim 1 wherein R is cyclo alkyl. 3. A compound of claim 1 wherein R is lower alkenyl. 4. The compound of the following formula 8 002m Il/ (CHz)aC=CH-P S-CHSC2H5 CH} 5. The com-pound ofthe following formula S OCZHJ 0112::011-1 s-oH -sc2H, (1H, 6'.- The. compound. of; the following formula S OC2H5 soH-s02m 2m. 7. The compound of thefollowing formula s 00in,

s-orps-on,

CH 8. The compound, of. the following formula I s 00 m, H l5 CH1 \s-om-s-cfi References Cited in the file of thispatent UNITED STATES PATENTS 2,8813201 Schrad'er Apr. 7, 1959 2,918,488 Schrader Dec. 22, 1959 FOREIGN PATENTS 1,032,247 Germany June 19, 1958 1 :UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION "Patent Noe 3,074,991 January 22, 1963 Gerhard Schrader It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1 line 38, for "ether" read thioether column 2 line 30, for "2 grams" read 22 grams line 31., for "ethyl ester" read thioether column 3, last line in the structural formula of claim I for CH read CH Signed and sealed this 19th day of November 1963;

(SEAL) EDWIN Le aawoms Attest:

ERNEST W; SWIDER Attesting Officer Ac t Commissioner of Patents 

1. A DITHIOPHOSPHONIC ACID ESTER OF THE FOLLOWING GENERAL FORMULA 